CN113130983B - Solid electrolyte and solid lithium ion battery - Google Patents
Solid electrolyte and solid lithium ion battery Download PDFInfo
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- CN113130983B CN113130983B CN201911395266.XA CN201911395266A CN113130983B CN 113130983 B CN113130983 B CN 113130983B CN 201911395266 A CN201911395266 A CN 201911395266A CN 113130983 B CN113130983 B CN 113130983B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
In order to overcome the problem of lithium dendrites existing in the existing solid electrolyte, the invention provides a solid electrolyte which is characterized by comprising a polymer and an additive, wherein the additive comprises a compound shown in the following structural formula 1:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, fluorine or a group containing 1 to 5 carbon atoms. Meanwhile, the invention also discloses a solid lithium ion battery comprising the solid electrolyte. The solid electrolyte provided by the invention can inhibit the growth of lithium dendrites in the charging and discharging processes, and improves the cycle performance.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a solid electrolyte and a solid lithium ion battery.
Background
Compared with traditional electrochemical energy devices such as lead-acid batteries and nickel-chromium batteries, the lithium ion batteries have the advantages of high energy density, high working voltage, no memory effect, long cycle life, environmental friendliness and the like, and are the most widely applied commercial energy storage systems. Although the traditional liquid lithium ion battery has good ionic conductivity and wettability, the traditional liquid lithium ion battery also has the safety problems of poor thermal stability, flammability, easy liquid leakage and the like. The current lithium ion battery system taking graphite as the cathode is optimized in mass production for many years, the energy density is difficult to exceed 300Wh/kg, and the requirement of the market on high endurance mileage is difficult to meet. Lithium metal negative electrode batteries of high theoretical energy density, such as Li-S and Li-O 2 System, etc., the high nickel and high voltage ternary anode material is provided with a silicon and silicon carbon cathode lithium ion battery to enter the sight. However, on the one hand, the conventional organic liquid electrolyte is easily decomposed on the surface of lithium metal, resulting in shortening the battery life; meanwhile, the liquid electrolyte can not effectively inhibit the growth of lithium dendrites, thereby bringing about the problems of short circuit of the battery, thermal runaway and even fire and explosion,on the other hand, the problems of volume expansion of the electrode material in use and the like all present challenges to the design of the battery.
A solid electrolyte having a higher energy density and excellent safety performance becomes a potentially best approach to solve the above-described problems instead of a liquid electrolyte. The polymer solid-state battery has good interface contact with electrode materials, is compatible with the existing lithium ion battery production equipment, and is a solid-state battery system which is most likely to realize large-scale application. However, the polymer electrolyte uses relatively flexible organic matters, and the interface contact between the electrode and the electrolyte in the lithium battery is relatively good, but the lithium battery has the problems of low ionic conductivity and incapability of inhibiting lithium dendrite. When the metal lithium negative electrode has defects or is uneven or has poor interface contact in the preparation process, lithium dendrite can be generated, so that the cycle performance of the battery is attenuated and loses efficacy, and meanwhile, the yield is reduced.
Therefore, it is highly desirable to develop a polymer solid electrolyte that can withstand the defects of lithium metal and improve the yield and life of the battery.
Disclosure of Invention
The invention provides a solid electrolyte and a solid lithium ion battery, aiming at the problem that the cycle performance of the battery is attenuated and fails due to the growth of lithium dendrite in the existing solid electrolyte.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the present invention provides a solid electrolyte comprising a polymer and an additive, the additive comprising a compound represented by the following structural formula 1:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, fluorine or a group containing 1 to 5 carbon atoms.
Optionally, the additive is dispersed on the surface and inside the solid electrolyte.
Optionally, the group containing 1 to 5 carbon atoms is selected from a hydrocarbon group, a fluorinated hydrocarbon group, an oxygen-containing hydrocarbon group, a silicon-containing hydrocarbon group, or a cyano-substituted hydrocarbon group.
Optionally, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, fluoro, methyl, ethyl, trimethylsiloxy, cyano or trifluoromethyl.
Optionally, the compound shown in the structural formula 1 is selected from one or more of the following compounds:
optionally, the mass percentage of the compound shown in the structural formula 1 is 0.01-20% based on 100% of the total mass of the solid electrolyte.
Optionally, the mass percentage of the compound shown in the structural formula 1 is 0.01-10% based on 100% of the total mass of the solid electrolyte.
Optionally, the polymer is a polar polymer, and the polymer includes a polymer obtained by polymerizing at least one of alkylene oxide monomers, siloxane monomers, olefin monomers, acrylate monomers, carboxylic ester monomers, carbonate monomers, amide monomers, and nitrile monomers, and a halide thereof;
the mass percentage of the polymer is 10-90% based on the total mass of the solid electrolyte being 100%.
Optionally, the solid electrolyte further comprises a lithium salt, wherein the lithium salt comprises LiBr, liI, liClO 4 、LiBF 4 、LiPF 6 、LiSCN、LiB 10 Cl 10 、LiCF 3 SO 3 、LiCF 3 CO 2 、LiBF 2 C 2 O 4 、LiB(C 2 O 4 ) 2 、LiN(SO 2 CF 3 ) 2 、LiN(SO 2 F) 2 、LiN(SO 2 F)(SO 2 CF 3 )、LiC(SO 2 CF 3 ) 3 、LiPF 2 (C 2 O 4 ) One or more of;
the lithium salt accounts for 10-80% of the total mass of the solid electrolyte as 100%.
Optionally, the solid electrolyte further includes an inorganic filler, and the inorganic filler includes LiF, liCl, li 2 CO 3 、SiO 2 、Al 2 O 3 、TiO 2 、ZrO 2 、MgO、Li 7 La 3 Zr 2 O 12 、Li x La 3 Zr y A 2-y O 12 Sulfide, li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 、Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 、Li 2.88 PO 3.73 N 0.14 One or more of montmorillonite, kaolin and diatomite, wherein A is one of Ta, al and Nb, x is more than or equal to 6 and less than or equal to 7, and y is more than or equal to 0.5 and less than or equal to 2;
the inorganic filler accounts for 0-40% of the total mass of the solid electrolyte by 100%.
Optionally, the solid electrolyte further comprises a solvent, wherein the solvent comprises one or more of carbonate, carboxylic ester and fluorinated solvent;
the mass percentage of the solvent is 0-10% based on 100% of the total mass of the solid electrolyte.
In another aspect, the present invention provides a solid-state lithium-ion battery comprising a positive electrode, a negative electrode, and a solid-state electrolyte as described above, the solid-state electrolyte being located between the positive electrode and the negative electrode.
Optionally, the negative electrode comprises a negative active material, and the negative active material comprises lithium titanate, a carbon material, and Li X Fe 2 O 3 、Li y WO 2 Lithium metal, lithium alloy, silicon alloy, tin alloy, metal oxideOne or more of the substances, conductive polymers and Li-Co-Ni-based materials, wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1.
Optionally, the negative active material is lithium metal.
According to the solid electrolyte provided by the invention, the compound shown in the structural formula 1 is added into the polymer, the compound can be uniformly dispersed and compositely fixed in the polymer, and different from the traditional liquid electrolyte, only the compound shown in the structural formula 1 positioned on the solid electrolyte interface can react with a negative electrode during battery formation, so that a uniform interface layer is formed on the surface of the negative electrode, the interface layer has the characteristic of conducting lithium ions, the migration rate of the lithium ions at the interface tends to be uniform, the migration rate gradient is reduced, the uniform insertion/deposition of lithium is facilitated, and the compound shown in the structural formula 1 in the solid electrolyte is in an unreacted state. Meanwhile, an interface layer generated by the reaction of the compound shown in the structural formula 1 and the negative electrode has certain mechanical strength and can play a role in inhibiting the generation of lithium dendrites. On the other hand, in the process of charging and discharging of the battery, if lithium dendrite is generated, when the lithium dendrite enters the solid electrolyte, the compound shown in the structural formula 1 in the solid electrolyte reacts with the lithium dendrite to further generate a passivation film with high mechanical strength, and resistance is applied to lithium dendrite sites, so that the growth of the lithium dendrite is further inhibited, and the cycle performance of the solid lithium ion battery is improved.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
An embodiment of the present invention provides a solid electrolyte including a polymer and an additive, the additive including a compound represented by the following structural formula 1:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, fluorine or a group containing 1 to 5 carbon atoms.
The compound shown in the structural formula 1 is added into the polymer, the compound can be uniformly dispersed and compounded in the polymer, and different from the traditional liquid electrolyte, only the compound shown in the structural formula 1 positioned on the interface of the solid electrolyte can react with a negative electrode during battery formation, so that a uniform interface layer is formed on the surface of the negative electrode, the interface layer has the characteristic of conducting lithium ions, the migration rate of the lithium ions at the interface tends to be uniform, the migration rate gradient is reduced, the uniform intercalation/deposition of lithium is facilitated, and the compound shown in the structural formula 1 in the solid electrolyte is in an unreacted state. Meanwhile, an interface layer generated by the reaction of the compound shown in the structural formula 1 and the negative electrode has certain mechanical strength and can play a role in inhibiting the generation of lithium dendrites. On the other hand, in the process of charging and discharging of the battery, if lithium dendrite is generated, when the lithium dendrite enters the solid electrolyte, the compound shown in the structural formula 1 in the solid electrolyte reacts with the lithium dendrite to further generate a passivation film with high mechanical strength, and resistance is applied to lithium dendrite sites, so that the growth of the lithium dendrite is further inhibited, and the cycle performance of the solid lithium ion battery is improved.
In some embodiments, the additive is dispersed on the surface and within the solid electrolyte.
In some embodiments, the 1-5 carbon atom-containing group is selected from a hydrocarbon group, a fluorinated hydrocarbon group, an oxygen-containing hydrocarbon group, a silicon-containing hydrocarbon group, or a cyano-containing substituted hydrocarbon group.
In some embodiments, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, fluoro, methyl, ethyl, trimethylsiloxy, cyano or trifluoromethyl.
In some embodiments, the compound of formula 1 is selected from one or more of the following compounds:
the above are some of the claimed compounds, but not limited thereto, and should not be construed as limiting the present invention.
In some embodiments, the compound represented by the structural formula 1 is contained in an amount of 0.01 to 20% by mass based on 100% by mass of the total mass of the solid electrolyte.
In a preferred embodiment, the compound represented by the structural formula 1 is contained in an amount of 0.01 to 10% by mass based on 100% by mass of the total mass of the solid electrolyte.
In a more preferred embodiment, the compound represented by the structural formula 1 is contained in an amount of 0.05 to 10% by mass based on 100% by mass of the total mass of the solid electrolyte.
If the content of the compound shown in the structural formula 1 is too low, the compound is not enough to react with lithium dendrite generated in the electrochemical process of the solid-state lithium ion battery, the effect of inhibiting the lithium dendrite is poor, and the performance of the solid-state lithium ion battery is difficult to improve; if the content of the compound shown in the structural formula 1 is too much, the deposition thickness of an interface layer generated by the reaction of the compound positioned on the interface of the solid electrolyte and the negative electrode is too large, the lithium ion conductivity of the too thick interface layer is reduced, the migration resistance of lithium ions in the interface layer is increased, the polarization of the solid lithium ion battery in the charging and discharging process is serious, the improvement of the cycle stability of the solid lithium ion battery is not facilitated, the internal resistance of the battery is increased, and the initial capacity is reduced.
In some embodiments, the polymer is a polar polymer.
The lithium salt is dissolved and dissociated by polar groups on the polymer chain under the action of Lewis acid and base, and lithium ions are transmitted by the movement of the polymer chain.
In some embodiments, the polymer includes a polymer polymerized from at least one of alkylene oxide monomers, siloxane monomers, olefin monomers, acrylate monomers, carboxylate monomers, carbonate monomers, amide monomers, nitrile monomers, and halides thereof;
the mass percentage of the polymer is 10-90% based on the total mass of the solid electrolyte being 100%.
In some embodiments, the solid electrolyte further comprises a lithium salt including LiBr, liI, liClO 4 、LiBF 4 、LiPF 6 、LiSCN、LiB 10 Cl 10 、LiCF 3 SO 3 、LiCF 3 CO 2 、LiBF 2 C 2 O 4 、LiB(C 2 O 4 ) 2 、LiN(SO 2 CF 3 ) 2 、LiN(SO 2 F) 2 、LiN(SO 2 F)(SO 2 CF 3 )、LiC(SO 2 CF 3 ) 3 、LiPF 2 (C 2 O 4 ) One or more of (a).
The lithium salt accounts for 10-80% of the total mass of the solid electrolyte as 100%.
In some embodiments, the solid electrolyte further comprises an inorganic filler comprising LiF, liCl, li 2 CO 3 、SiO 2 、Al 2 O 3 、TiO 2 、ZrO 2 、MgO、Li 7 La 3 Zr 2 O 12 、Li x La 3 Zr y A 2-y O 12 Sulfide, li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 、Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 、Li 2.88 PO 3.73 N 0.14 One or more of montmorillonite, kaolin and diatomite, wherein A is one of Ta, al and Nb, x is more than or equal to 6 and less than or equal to 7, and y is more than or equal to 0.5 and less than or equal to 2;
by adding the inorganic filler to the solid electrolyte, the mechanical properties of the solid electrolyte can be further improved, and the growth of lithium dendrites can be inhibited. Meanwhile, the inorganic filler can reduce the crystallinity of the polymer and improve the chain segment moving capability of the polymer, thereby improving the migration speed of lithium ions in the polymer, bringing higher ionic conductivity to the solid electrolyte and contributing to reducing the polarization in the electrochemical process.
The inorganic filler accounts for 0-40% of the total mass of the solid electrolyte by 100%.
When the weight content of the inorganic filler is too high, the mechanical strength of the solid electrolyte is affected and the film-forming property becomes poor.
The median particle diameter D50 of the inorganic filler is 5 nm-5 mu m.
In some embodiments, the solid state electrolyte further comprises a porous skeleton, the polymer being supported on the porous skeleton.
In some embodiments, the porous scaffold is selected from a bacterial cellulose membrane.
In some embodiments, the solid-state electrolyte further comprises a solvent comprising one or more of a carbonate, a carboxylate, a fluorinated solvent;
the mass percentage of the solvent is 0-10% based on 100% of the total mass of the solid electrolyte.
In another aspect, the present invention provides a solid-state lithium-ion battery comprising a positive electrode, a negative electrode, and a solid-state electrolyte as described above, the solid-state electrolyte being located between the positive electrode and the negative electrode.
In some embodiments, the positive electrode comprises a positive active material comprising LiNi x Co y Mn z L (1-x-y-z) O 2 、LiCo x’ L (1-x’) O 2 、LiNi x” L’ y’ Mn (2-x”-y’) O 4 、Li z’ MPO 4 At least one of; wherein L is Al, sr, mg, ti, ca, zr, zn, si or Fe; x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x + y + z is more than 0 and less than or equal to 1<x’≤1，0.3≤x”Not more than 0.6, not less than 0.01 and not more than 0.2; l' is Co, al, sr, mg, ti, ca, zr, zn, si or Fe; z' is more than or equal to 0.5 and less than or equal to 1, and M is at least one of Fe, mn and Co.
Specifically, the positive active material is selected from one or more of lithium cobaltate, nickel cobalt aluminum, nickel cobalt manganese, lithium iron manganese phosphate, lithium manganate and lithium iron phosphate.
In some embodiments, the positive electrode further comprises a positive electrode binder and a positive electrode conductive agent.
In some embodiments, the negative electrode includes a negative active material including Lithium Titanate (LTO), a carbon material, li X Fe 2 O 3 、Li y WO 2 One or more of lithium metal, lithium alloy, silicon alloy, tin alloy, metal oxide, conductive polymer and Li-Co-Ni-based material, wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1.
In some preferred embodiments, the negative active material is lithium metal.
The carbon material includes non-graphitized carbon and graphitized carbon.
The metal oxide comprises SnO and SnO 2 、PbO、Pb 2 O 3 、Pb 3 O 4 、Sb 2 O 3 、Sb 2 O 4 、Sb 2 O 5 、GeO、GeO 2 、Bi 2 O 3 、Bi 2 O 4 、Bi 2 O 5 And titanium oxide
The conductive polymer comprises polyacetylene.
In some embodiments, the negative electrode further comprises a negative electrode binder and a negative electrode conductive agent.
The solid-state lithium ion battery adopts the solid electrolyte, so that the solid-state lithium ion battery has better circulation stability, and can effectively avoid battery short circuit and polarization voltage improvement caused by lithium dendrites.
The present invention will be further illustrated by the following examples.
Example 1
This example is used to illustrate the preparation method of the solid electrolyte and the solid lithium ion battery disclosed in the present invention, and includes the following operation steps:
preparation of polymer solid electrolyte:
the additive used was Compound 1, 1.0g of polyethylene oxide (PEO) having a weight-average molecular weight of 60W, 0.41g of LiN (SO) 2 CF 3 ) 2 Dissolve in 5g acetonitrile, add 0.029g Compound 1, stir until the solid is completely dissolved. And (3) placing the obtained polymer solution on a coating machine, automatically scraping and coating by using a scraper, drying for 8 hours at normal temperature in vacuum, and drying for 12 hours at 80 ℃ in vacuum to obtain the polymer solid electrolyte with the particle size of 40 microns. The content of compound 1 in the electrolyte was 2% by weight based on the total weight of the electrolyte.
Preparing a solid lithium ion battery:
and (3) positive electrode: mixing LiFePO 4 The active material, the conductive carbon black and the polymer electrolyte are mixed in a mass ratio of 80. The obtained slurry is uniformly coated on an aluminum foil, dried at 80 ℃ until no obvious liquid exists, and then dried for 12 hours at 100 ℃ under vacuum.
Negative electrode: lithium metal was used as the negative electrode.
Preparing a solid lithium ion battery: the 2032 button cell is assembled in the order of cathode casing-shrapnel-gasket-cathode-polymer solid electrolyte-anode-cathode casing.
Example 2
This example is used to illustrate the preparation method of the solid electrolyte and the solid lithium ion battery disclosed in the present invention, which includes most of the operation steps in example 1, and the differences are as follows:
polyethylene oxide (PEO) in example 1 was replaced with polypropylene carbonate (PPC).
Example 3
This example is used to illustrate the preparation method of the solid electrolyte and the solid lithium ion battery disclosed in the present invention, which includes most of the operation steps in example 1, and the differences are as follows:
by using LiCF 3 SO 3 Instead of LiN (SO) as the lithium salt in example 1 2 CF 3 ) 2 。
Example 4
This example is used to illustrate the preparation method of the solid electrolyte and the solid lithium ion battery disclosed in the present invention, which includes most of the operation steps in example 1, and the differences are as follows:
in the operation of preparing the polymer solid electrolyte, 0.1656g of nano alumina with the size of 8-12nm and d50=10nm is added into a polymer solution, ultrasonic dispersion is carried out, after the ultrasonic dispersion, the solid electrolyte solution is placed into a polytetrafluoroethylene template for drying, volatilization is carried out for 4 hours at normal temperature, and vacuum drying is carried out for 6 hours at 60 ℃ to obtain the solid polymer electrolyte.
Example 5
This example is used to illustrate the preparation method of the solid electrolyte and the solid lithium ion battery disclosed in the present invention, which includes most of the operation steps in example 1, and the differences are as follows:
in the operation of preparing the polymer solid electrolyte, after the preparation of the solid electrolyte solution is finished, a bacterial cellulose membrane is obtained, the porosity of the bacterial cellulose membrane is 85vol% calculated by an Archimedes method, the solid electrolyte solution is soaked in the bacterial cellulose membrane, the solid electrolyte solution is soaked after the solvent is volatilized at normal temperature, the operation is repeated until the pores are completely filled with the polymer, and the solid electrolyte is obtained by vacuum drying for 6 hours at 60 ℃, wherein the average thickness of the solid electrolyte membrane is 52 mu m.
Example 6
This example is used to illustrate the preparation method of the solid electrolyte and the solid lithium ion battery disclosed in the present invention, including most of the operation steps in example 3, and the differences are as follows:
using LiFe 0.5 Mn 0.5 PO 4 LiFePO as an alternative to the positive electrode active material in example 1 4 。
Example 7
This example is used to illustrate the preparation method of the solid electrolyte and the solid lithium ion battery disclosed in the present invention, which includes most of the operation steps in example 1, and the differences are as follows:
adopt the structureIs of the formula
Compound 3 replaces compound 1 in example 1.
Example 8
This example is used to illustrate the preparation method of the solid electrolyte and the solid lithium ion battery disclosed in the present invention, which includes most of the operation steps in example 1, and the differences are as follows:
adopts a structural formula as
Compound 4 replaces compound 1 in example 1.
Example 9
This example is used to illustrate the preparation method of the solid electrolyte and the solid lithium ion battery disclosed in the present invention, and includes most of the operation steps in example 1, and the differences are that:
adopts a structural formula as
Compound 8 replaces compound 1 in example 1.
Example 10
This example is used to illustrate the preparation method of the solid electrolyte and the solid lithium ion battery disclosed in the present invention, which includes most of the operation steps in example 1, and the differences are as follows:
adopts a structural formula as
Compound 9 replaces the additive in example 1.
Comparative example 1
This comparative example is used for comparative illustration of the preparation method of the solid electrolyte and the solid lithium ion battery disclosed in the present invention, and includes most of the operation steps in example 1, except that:
in the operation of "preparation of polymer solid electrolyte", the compound represented by the formula 1 is not added to the polymer solution.
Comparative example 2
This comparative example is used for comparative illustration of the preparation method of the solid electrolyte and the solid lithium ion battery disclosed in the present invention, which includes most of the operation steps in example 6, except that:
in the operation of "preparation of polymer solid electrolyte", the compound represented by the formula 1 is not added to the polymer solution.
Performance testing
The following performance tests were performed on the solid electrolyte and the solid lithium ion battery prepared in examples 1 to 10 and comparative examples 1 and 2:
the solid lithium ion batteries prepared in the above examples 1 to 10 and comparative examples 1 and 2 were subjected to a charge-discharge cycle test using a blue tester at a temperature of 60 ℃. Wherein the solid lithium ion batteries of examples 1 to 5, 7 to 10 and comparative example 1 were charged to 3.8V at a current of 0.2C, then were charged at constant voltage until the current dropped to 0.20mA, and then were discharged at constant current of 0.2C to 2.8V, and were cycled for 200 weeks; the solid-state lithium ion batteries of example 6 and comparative example 2 were charged to 4.2V at a current of 0.2C, then charged at a constant voltage until the current was reduced to 0.20mA, and then discharged to 3.0V at a current of 0.2C, and the capacity retention rate of the batteries was calculated according to the formula "capacity retention rate = 300-week discharge capacity/1-week discharge capacity × 100%", after 200 cycles. The first-turn coulombic efficiency of the battery, and the average coulombic efficiency for N cycles = the sum of the coulombic efficiencies for N cycles/N were calculated according to the formula "coulombic efficiency = discharge capacity per one week/charge capacity per one week × 100%",
the test results obtained are filled in Table 1.
TABLE 1
As can be seen from the comparison of the test results of comparative example 1 and example 1 in table 1, when 2wt% of compound 1 is added as an additive to the solid electrolyte, although the first week coulombic efficiency of example 1 is lower than that of comparative example 1, the cycle average coulombic efficiency is much higher than that of comparative example 1, which is mainly because the additive participates in the electrochemical reaction on the surface of the negative electrode in the first week, and a new interfacial layer is formed on the surface of the metallic lithium. Comparative example 1 short-circuiting occurred at 120 cycles due to lithium metal dendrite growth piercing through the electrolyte, whereas example 1 had a capacity retention of 80% or more after 480 cycles. The same data from example 6 and comparative example 2 also validate the above conclusions.
As can be seen from the results of comparing the cell performances of examples 1 to 10, the average coulombic efficiency at 60 ℃ of 0.2C of the cells prepared by using the solid polymer electrolyte of the present invention is more than 98.2%, and the average coulombic efficiency is calculated by LiFePO 4 The capacity retention rate of the battery which is the positive electrode is more than 80 percent at 0.2C cycle, and the cycle number is more than 456 weeks, which shows that the addition of the additive plays an important role in inhibiting the generation of lithium dendrites and prolonging the service life of the solid lithium ion battery. As can be seen from the test results of example 6 and comparative example 2, different positive electrode materials, such as LiFe, were used 0.5 Mn 0.5 PO 4 When the solid electrolyte is used as a positive electrode material, the cycle performance of the solid lithium ion battery is also remarkably improved, which shows that the solid electrolyte provided by the invention is suitable for different positive electrode material systems. Comparing example 1 with example 5, it can be found that when the porous skeleton is introduced into the electrolyte, the cycle capacity retention rate of the battery is improved by more than 80%, because the introduction of the porous skeleton improves the mechanical strength of the electrolyte, reduces the glass transition problem of the electrolyte, and more effectively inhibits the growth of the dendrite of the negative electrode.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A solid state electrolyte comprising a polymer and an additive, the additive comprising a compound represented by the following structural formula 1:
structural formula 1
Wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, fluorine or a group containing 1 to 5 carbon atoms;
the mass percentage of the compound shown in the structural formula 1 is 0.01-2% based on 100% of the total mass of the solid electrolyte.
2. The solid electrolyte of claim 1, wherein the additive is dispersed on the surface and in the interior of the solid electrolyte.
3. The solid electrolyte according to claim 1, wherein the group having 1 to 5 carbon atoms is selected from a hydrocarbon group, a fluorinated hydrocarbon group, an oxygen-containing hydrocarbon group, a silicon-containing hydrocarbon group, or a cyano-containing substituted hydrocarbon group.
4. The solid state electrolyte of claim 1, wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, fluoro, methyl, ethyl, trimethylsiloxy, cyano or trifluoromethyl.
5. The solid electrolyte of claim 1, wherein the compound of formula 1 is selected from one or more of the following compounds:
compound 1 Compound 2
Compound 3 Compound 4
Compound 5 Compound 6
Compound 7 Compound 8
Compound 9.
6. The solid electrolyte according to claim 1, wherein the polymer is a polar polymer, and the polymer comprises a polymer obtained by polymerizing at least one of alkylene oxide monomers, siloxane monomers, olefin monomers, acrylate monomers, carboxylate monomers, carbonate monomers, amide monomers, nitrile monomers, and a halide thereof;
the mass percentage of the polymer is 10-90% based on the total mass of the solid electrolyte being 100%.
7. The solid state electrolyte of claim 6, further comprising a solvent comprising one or more of a carbonate, a carboxylate, a fluorinated solvent;
the mass percentage of the solvent is 0-10% based on 100% of the total mass of the solid electrolyte.
8. A solid-state lithium ion battery, characterized by comprising a positive electrode, a negative electrode and the solid-state electrolyte according to any one of claims 1 to 7, wherein the solid-state electrolyte is positioned between the positive electrode and the negative electrode.
9. The solid state lithium ion battery of claim 8, wherein the negative electrode comprises a negative active material comprising lithium titanate, carbon materials, li X Fe 2 O 3 、Li y WO 2 One or more of lithium metal, lithium alloy, silicon alloy, tin alloy, metal oxide, conductive polymer and Li-Co-Ni-based material, wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1.
10. The solid state lithium ion battery of claim 9, wherein the negative active material is lithium metal.
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| CN201911395266.XA CN113130983B (en) | 2019-12-30 | 2019-12-30 | Solid electrolyte and solid lithium ion battery |
| PCT/CN2020/136014 WO2021135900A1 (en) | 2019-12-30 | 2020-12-14 | Solid electrolyte and solid lithium-ion battery |
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